EP0771830B1 - Härtbare Zusammensetzung enthaltend Cycloolefin, Silan und Füllstoff - Google Patents

Härtbare Zusammensetzung enthaltend Cycloolefin, Silan und Füllstoff Download PDF

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Publication number
EP0771830B1
EP0771830B1 EP96810707A EP96810707A EP0771830B1 EP 0771830 B1 EP0771830 B1 EP 0771830B1 EP 96810707 A EP96810707 A EP 96810707A EP 96810707 A EP96810707 A EP 96810707A EP 0771830 B1 EP0771830 B1 EP 0771830B1
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Prior art keywords
alkyl
component
composition according
unsubstituted
substituted
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French (fr)
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EP0771830A2 (de
EP0771830A3 (de
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Frans Setiabudi
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a composition
  • a composition comprising a strained cycloolefin, a ROMP catalyst, a filler and a silane; a method for producing a metathesis polymer from this composition and the use of this composition as a covering material for electrical or electronic components.
  • Filled epoxy resin systems are often used as wrapping materials in the manufacture of electrical and electronic components.
  • Such epoxy resin casting compounds such as are disclosed, for example, in EP-A-348 193 or EP-A-540 467, have disadvantages with regard to toughness and heat stability.
  • cycloolefins which can be polymerized by means of ring-opening metathesis polymerization (ROMP) should in principle be suitable for electrical applications.
  • ring-opening metathesis polymerization ring-opening metathesis polymerization
  • Such systems are described for example in WO 96/16100, WO 96/20235 or in EP-A-348 852.
  • fillers causes a sharp deterioration in the mechanical and electrical properties of these materials.
  • EP-A-0 349 855 describes a shaped body made of fillers and polymers which have been obtained by a metathesis reaction.
  • the catalyst system consists of two components; on the one hand from tungsten, molybdenum, rhenium or tantalum halides and on the other hand from an organometallic activator such as tri-n-octyl aluminum.
  • strained cycloolefins are understood to mean all cycloolefins with the exception of cyclohexene and its derivatives, which cannot be polymerized using the ring-opening metathesis.
  • the strained cycloolefins can be monocyclic or polycyclic fused or bridged ring systems, for example with two to four rings, which are unsubstituted or substituted and heteroatoms, such as O, S, N or Si, in one or more Rings and / or fused aromatic or heteroaromatic rings, such as o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene.
  • the individual cyclic rings can contain 3 to 16, preferably 3 to 12 and particularly preferably 3 to 8 ring members.
  • the strained cycloolefins can contain further non-aromatic double bonds, depending on the ring size, preferably 2 to 4 such additional double bonds.
  • the ring substituents are inert, i.e. these substituents do not affect the chemical stability and the thermal stability of the ROMP catalysts.
  • crosslinked polymers can also form, depending on the reaction conditions, the monomer chosen and the amount of catalyst.
  • Fused-on alicyclic rings preferably contain 3 to 8, particularly preferably 4 to 7 and particularly preferably 5 or 6 ring C atoms.
  • composition according to the invention can contain further olefins capable of metathesis for crosslinking or for regulating the molecular weight, advantageously in amounts of up to 40 mol%, preferably 0.01 to 30 mol% and particularly preferably 0.1 to 20 mol%, based on the total amount of cycloolefins and olefins present.
  • Suitable olefins capable of metathesis are, for example, cyclooctadiene, cyclooctatriene, norbonadiene or acetylnorbornene.
  • Compounds such as 2-butene-1,4-diol, as described in Feast, W.J., Harrison, B, J. Mol. Catal. 65, 63 (1991), or 1-hexene (rearrangements) is suitable.
  • alkyl, alkenyl and alkynyl groups can be straight-chain or branched. The same also applies to the or each alkyl part of alkoxy, alkylthio, alkoxycarbonyl and other alkyl-containing groups.
  • These alkyl groups preferably contain 1 to 12, particularly preferably 1 to 8 and particularly preferably 1 to 4 carbon atoms.
  • alkenyl and alkynyl groups preferably contain 2 to 12, particularly preferably 2 to 8 and particularly preferably 2 to 4 carbon atoms.
  • Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups.
  • Hydroxyalkyl includes, for example, hydroxymethyl, hydroxyethyl,. Hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl, 1-hydroxyisobutyl, 1-hydroxy-sec.-butyl, 1-hydroxytert.-butyl and the various hydroxyl-substituted isomeric pentyl-, hexyl-, heptyl- .
  • Haloalkyl includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl as well as halogenated, especially fluorinated or chlorinated isopropyl, n- Propyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups and the various isomeric halogenated pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and e
  • alkenyl includes propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec- 2-enyl, isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl.
  • Cycloalkyl is preferably C 5 -C 8 cycloalkyl, in particular C 5 or C 6 cycloalkyl. Some examples are cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Cyanoalkyl includes, for example, cyanomethyl (methyl nitrile), cyanoethyl (ethyl nitrile), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl, 1-cyanoisobutyl, 1-cyano-sec.-butyl, 1-cyano- tert-butyl and the various isomeric cyanopentyl and hexyl radicals.
  • Aralkyl preferably contains 7 to 12 carbon atoms and particularly preferably 7 to 10 carbon atoms.
  • it can be benzyl, phenethyl, 3-phenylpropyl, ⁇ -methylbenzyl, 4-phenylbutyl and ⁇ , ⁇ -dimethylbenzyl.
  • Aryl preferably contains 6 to 10 carbon atoms. It can be, for example, phenyl, pentalinyl, indenyl, naphthyl, azulinyl and anthryl.
  • Heteroaryl preferably contains 4 or 5 carbon atoms and one or two heteroatoms from the groups O, S and N. It can be, for example, pyrrolyl, furanyl, thiophenyl, oxazolyl, thiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, purinyl and Trade quinolyl.
  • Heterocycloalkyl preferably contains 4 or 5 carbon atoms and one or two heteroatoms from the group O, S and N. It can be, for example, oxiranyl, azirinyl, 1,2-oxathiolanyl, pyrazolinyl, pyrrolidinyl, piperidyl, piperazyl, morpholinyl, tetrahydrofuranyl and Act tetrahydrothiophenyl.
  • Alkoxy is, for example, methoxy, ethoxy, propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy and tert-butyloxy.
  • Alkali metal is to be understood in the context of the present invention as lithium, sodium, potassium, rubidium and cesium, in particular lithium, sodium and potassium.
  • alkaline earth metal is to be understood as meaning beryllium, magnesium, calcium, strontium and barium, in particular magnesium and calcium.
  • halogen means fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
  • Compounds of the formula II which are particularly suitable in the composition according to the invention are those in which Q 2 is hydrogen.
  • Norbornene and norbomene derivatives in particular dicyclopentadiene and dicyclopentadiene derivatives, are particularly preferred as component (a).
  • Preferred norbornene derivatives are the compounds of the formulas III, IV, V and VI wherein X 3 is -CHR 16 -, oxygen or sulfur, R 14 and R 15 independently of one another are hydrogen, -CN, trifluoromethyl, (CH 3 ) 3 SiO-, (CH 3 ) 3 Si or -COOR 17 and R 16 and R 17 independently represent hydrogen, C 1 -C 12 alkyl, phenyl or benzyl; X 4 is -CHR 19 -, oxygen or sulfur, R 19 is hydrogen, C 1 -C 12 alkyl, phenyl or benzyl and R 18 is hydrogen, C 1 -C 6 alkyl or halogen; X 5 is -CHR 22 -, oxygen or sulfur, R 22 is hydrogen, C 1 -C 12 alkyl, phenyl or benzyl and R 20 and R 21 independently of one another are hydrogen, CN, trifluoromethyl, (CH 3 ) 3 SiO-, (CH 3 ) 3 represent
  • Suitable compounds of the formula II are the following cycloolefins:
  • the strained cycloolefins contain only carbon and hydrogen atoms, and are preferably 5- or 6-membered rings or ring systems with one to three 5- or 6-membered rings, for example norbomen, alkylated norbornenes and dicyclopentadiene ,
  • Dicyclopentadiene is particularly preferred as component (a).
  • ROMP catalysts ring-opening metathesis polymerization
  • These are, for example, complex metal halides, metallo-carbenes or coordination catalysts of the Ziegler-Natta type. All of these known ROMP catalysts can in principle be used as component (b) in the compositions according to the invention.
  • a ruthenium (+ II) complex salt or an osmium (+ II) complex salt, particularly preferably a ruthenium (+ II) complex salt, is preferably used as component (b).
  • moisture-insensitive ROMP catalysts e.g. the ruthenium (+ ll) and osmium (+ II) complex salts described in WO 96/16100 and WO 96/20235.
  • Component salt of formula III is therefore preferred as component (b) (R 29 R 30 R 31 P) x L y Me 2+ Z 1 - Z 2 - (III), wherein R 29 , R 30 and R 31 independently of one another are H, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, unsubstituted or with C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or C 1 -C 6 alkoxy substituted C 4 -C 12 cycloalkyl or cycloalkoxy, or C 6 -C 16 unsubstituted or substituted by C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or C 1 -C 6 alkoxy - aryl or C 6 -C 16 aryloxy, unsubstituted or or C 1 -C 6 alkyl, C 1 -C 6 haloalkyl or C 1 -C 6 -alkoxy-substit
  • the ligands L in the compounds of the formula III can be the same or different.
  • the ruthenium and osmium compounds of the formula III are known or by known processes from the metal halides (for example MeX 3 or [MeArenX 2 ] 2 by reaction with phosphines of the formula IV R 29 R 30 R 31 P (IV), wherein R 29 , R 30 , and R 31 have the same meaning as in formula (III), and ligand formers can be prepared.
  • metal halides for example MeX 3 or [MeArenX 2 ] 2 by reaction with phosphines of the formula IV R 29 R 30 R 31 P (IV), wherein R 29 , R 30 , and R 31 have the same meaning as in formula (III), and ligand formers can be prepared.
  • radicals R 29 , R 30 and R 31 are preferably identical radicals.
  • Sterically demanding radicals are also preferred, for example branched, in particular ⁇ -branched, alkyl or alkoxy or cyclic radicals.
  • R 29 , R 30 and R 31 can be linear or branched as alkyl and preferably contain 1 to 12, particularly preferably 1 to 8, and very particularly preferably 1 to 6 carbon atoms.
  • alkyl are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, the isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, Hexadecyl, heptadecyl, octadecyl and eicosyl.
  • Preferred examples are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, 1-, 2- or 3-pentyl and 1-, 2-, 3- or 4-hexyl.
  • R 29 , R 30 and R 31 can be linear or branched as alkoxy and preferably contain 1 to 12, particularly preferably 1 to 8, and very particularly preferably 1 to 6 carbon atoms.
  • alkoxy are methoxy, ethoxy, n- and i-propyloxy, n-, i- and t-butyloxy, the isomers of pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, Hexadecyloxy, heptadecyloxy, octadecyloxy and eicosyloxy.
  • Preferred examples are methoxy, ethoxy, n- and i-propyloxy, n-, i- and t-butyloxy, 1-, 2- or 3-pentyloxy and 1-, 2-, 3- or 4-hexyloxy.
  • R 29 , R 30 and R 31 are substituted, the substituents are preferably C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy.
  • Halogen is preferably Cl and particularly preferably F. Examples of preferred substituents are methyl, methoxy, ethyl, ethoxy and trifluoromethyl.
  • R 29 , R 30 and R 31 are preferably substituted with 1 to 3 substituents.
  • R 29 , R 30 and R 31 are cycloalkyl, it is preferably C 5 -C 8 cycloalkyl, and particularly preferably C 5 - or C 6 cycloalkyl.
  • Some examples are cyclobutyl, Cycloheptyl, Cyclooctyl and especially Cyclopentyl and Cyclohexyl.
  • Examples of substituted cycloalkyl are methyl, dimethyl, trimethyl, methoxy, dimethoxy, trimethoxy, trifluoromethyl, bistrifluoromethyl and tristrifluoromethylcyclopentyl and cyclohexyl.
  • R 29 , R 30 and R 31 are cycloalkyloxy, they are preferably C 5 -C 8 cycloalkyloxy, and particularly preferably C 5 - or C 6 cycloalkyloxy. Some examples are cyclobutyloxy, cycloheptyloxy, cyclooctyloxy and especially cyclopentyloxy and cyclohexyloxy. Examples of substituted cycloalkyl are methyl, dimethyl, trimethyl, methoxy, dimethoxy, trimethoxy, trifluoromethyl, bistrifluoromethyl and tristrifluoromethylcyclopentyloxy and cyclohexyloxy.
  • R 29 , R 30 and R 31 are aryl, it is preferably C 6 -C 12 aryl and particularly preferably phenyl or naphthyl.
  • substituted aryl are methyl, dimethyl, trimethyl, methoxy, dimethoxy, trimethoxy, trifluoromethyl, bistrifluoromethyl and tristrifluoromethylphenyl.
  • R 29 , R 30 and R 31 are aryloxy, it is preferably C 6 -C 12 aryloxy and particularly preferably unsubstituted or substituted phenyloxy or naphthyloxy.
  • substituted aryloxy are methyl, dimethyl, trimethyl, methyl isopropyl, isopropyl, diisopropyl, triisopropyl, tert-butyl, methyl tert-butyl, di (tert-butyl), tri (tert-butyl) -, methoxy, dimethoxy, trimethoxy, trifluoromethyl, bistrifluoromethyl and tristrifluoromethylphenyloxy.
  • R 29 , R 30 and R 31 are aralkyl, it is preferably C 7 -C 13 aralkyl, the alkylene group in the aralkyl preferably being methylene.
  • the aralkyl is particularly preferably benzyl.
  • substituted aralkyl are methyl, dimethyl, trimethyl, methoxy, dimethoxy, trimethoxy, trifluoromethyl, bistrifluoromethyl and tris (trifluoromethyl) benzyl.
  • R 29 , R 30 and R 31 are aralkyloxy, they are preferably unsubstituted or substituted C 7 -C 13 aralkyloxy, the alkylene group in aralkyloxy preferably being methylene.
  • Aralkyloxy is particularly preferably unsubstituted or substituted benzyloxy. Examples of substituted aralkyloxy are methyl, dimethyl, Trimethyl, methoxy, dimethoxy, trimethoxy, trifluoromethyl, bis (fluoromethyl) and tristrifluoromethylbenzyloxy.
  • R 29 , R 30 and R 31 are C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 4 -C 12 cycloalkyl, C 4 -C 12 cycloalkoxy, C 6 -C 16 aryl or C 6 -C 16 aryloxy.
  • Suitable phosphines of the formula IV are (C 6 H 5 ) 3 P, (C 6 H 5 CH 2 ) 3 P, (C 5 H 11 ) 3 P, (CH 3 ) 3 P, (C 2 H 5 ) 3 P, (nC 3 H 7 ) 3 P, (iC 3 H 7 ) 3 P, (nC 4 H 9 ) 3 P, (C 6 H 5 ) 2 HP, (C 6 H 5 CH 2 ) 2 HP, (C 5 H 11 ) 2 HP, (CH 3 ) 2 HP, (C 2 H 5 ) 2 HP, (nC 3 H 7 ) 2 HP, (iC 3 H 7 ) 2 HP, (nC 4 H 9 ) 2 HP, (C 6 H 5 ) H 2 P, (C 6 H 5 CH 2 ) H 2 P, (C 5 H 11 ) H 2 P, (CH 3 ) H 2 P, (C 2 H 5 ) H 2 P, (nC 3 H 7 ) H 2 P, (iC 3 H 7 )
  • Particularly preferred phosphines are triisopropylphosphine, tri-tert-butylphosphine and tricyclohexylphosphine.
  • the ligands L bonded to the metal atom in the compounds of the formula III can be photolabile or non-photolabile ligands.
  • the catalytic activity is achieved by exposure to light, ie when the catalyst is irradiated with light in the visible or ultraviolet range, the photolabile ligand is split off, a catalytically active species for metathesis polymerization being formed.
  • the photolabile ligands can be, for example, nitrogen (N 2 ), unsubstituted or monocyclic, substituted by OH, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 6 -C 12 aryl or halogen, polycyclic or condensed arenes having 6 to 24, preferably 6 to 18 and particularly preferably 6 to 12 carbon atoms or monocyclic heteroarenes, condensed heteroarenes, which are unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy or halogen or condensed arene heteroarenes having 3 to 22, preferably 4 to 16 and especially 4 to 10 C atoms and 1 to 3 heteroatoms selected from the group O, S and N; or aliphatic, cycloaliphatic, aromatic or araliphatic nitriles with 1 to 22, preferably 1 to 18, particularly preferably 1 to 12 and very particularly preferably unsubstituted or substituted with C 1 -
  • the preferred substituents are methyl, ethyl, methoxy, ethoxy, fluorine, chlorine and bromine.
  • the arenes and heteroarenes are preferably substituted with one to three radicals.
  • the heteroarenes the electron rich heteroarenes are preferred.
  • Some examples of arenes and heteroarenes are benzene, biphenyl, naphthalene, anthracene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene, fluoranthrene, furan, thiophene, pyrrole, pyridine, ⁇ -pyran, ⁇ -thiopyran, pyrimidine, pyrazine, indole, coumarone , Thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazines, thianthrene and purine.
  • Preferred arenes and heteroarenes are unsubstituted or substituted benzene, naphthalene, thiophene and benzthiophene.
  • the arene is particularly preferably unsubstituted or substituted with 1 to 3 C 1 -C 4 alkyl and the heteroarene is preferably thiophene.
  • the nitriles can be substituted, for example, with methoxy, ethoxy, fluorine or chlorine; the nitriles are preferably unsubstituted.
  • the alkyl nitriles are preferably linear. Some examples of nitriles are acetonitrile, propionitrile, butyronitrile, pentyl nitrile, hexyl nitrile, cyclopentyl and cyclohexyl nitrile, benzonitrile, methylbenzonitrile, benzyl nitrile and naphthyl nitrile.
  • the nitriles are preferably linear C 1 -C 4 alkyl nitriles or benzonitrile. Of the alkyl nitriles, acetonitrile is particularly preferred.
  • the photolabile ligands are N 2 , unsubstituted or substituted by one to three C 1 -C 4 alkyl benzene, thiophene, benzonitrile or acetonitrile.
  • non-photolabile ligand also referred to as a strongly coordinating ligand
  • the ligand does not dissociate from the catalyst, or only to an insignificant extent, when the catalyst is irradiated in the visible or near ultraviolet spectral range.
  • the non-photolabile ligands can be, for example, the heteroatoms O, S or N containing and solvating inorganic and organic compounds, which are often also used as solvents.
  • examples of such compounds are H 2 O, H 2 S, NH 3 ; optionally halogenated, especially fluorinated or chlorinated aliphatic or cycloaliphatic alcohols or mercaptans with 1 to 18, preferably 1 to 12 and particularly preferably 1 to 6 carbon atoms, aromatic alcohols or thiols with 6 to 18, preferably 6 to 12 carbon atoms, araliphatic Alcohols or thiols with 7 to 18, preferably 7 to 12, carbon atoms; Open-chain or cyclic and aliphatic, araliphatic or aromatic ethers, thioethers, sulfoxides, sulfones, ketones, aldehydes, carboxylic acid esters, lactones, optionally NC 1 -C 4 -mono- or -dialky
  • non-photolabile ligands examples include methanol, ethanol, n- and i-propanol, n-, i- and t-butanol, 1,1,1-trifluoroethanol, bistrifluoromethylmethanol, tristrifluoromethylmethanol, pentanol, hexanol, methyl- or ethylmercaptan, Cyclopentanol, cyclohexanol, cyclohexyl mercaptan, phenol, methylphenol, fluorophenol, phenyl mercaptan, benzyl mercaptan, benzyl alcohol, diethyl ether, dimethyl ether, diisopropyl ether, di-n- or di-t-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, diethylthioethoxide, diethylthioethoxide, dieth
  • the primary amines can correspond to the formula R 26 NH 2 , the secondary amines to the formula R 26 R 27 NH and the tertiary amines to the formula R 26 R 27 R 28 N, where R 26 is C 1 -C 18 alkyl, unsubstituted or with C 1 -C 4 alkyl or C 1 -C 4 -alkoxy-substituted C 5 - or C 6 cycloalkyl, or unsubstituted or C 1 -C 4 alkyl or C 1 -C 4 -alkoxy-substituted C 6 -C 18 Aryl or C 7 -C 12 aralkyl, R 27 independently has the meaning of R 26 or R 26 and R 27 together tetramethylene, pentamethylene, 3-oxa-1,5-pentylene or -CH 2 -CH 2 -NH -CH 2 -CH 2 - or -CH 2 -CH 2 -N (C 1 -C 4 alky
  • the alkyl preferably contains 1 to 12 and particularly preferably 1 to 6 carbon atoms.
  • the aryl preferably contains 6 to 12 carbon atoms and the aralkyl preferably contains 7 to 9 carbon atoms.
  • Examples of amines are methyl, dimethyl, trimethyl, ethyl, diethyl, triethyl, methylethyl, dimethylethyl, n-propyl, di-n-propyl, tri-n-butyl, cyclohexyl, phenyl - And benzylamine, as well as pyrrolidine, N-methylpyrrolidine, piperidine, piperazine, morpholine and N-methylmorpholine.
  • compositions according to the invention preferably contain, as component (b), a complex salt of the formula III in which L represents an arene, heteroarene, nitrile, nitrogen (N 2 ), alcohol, amine, CO, H 2 O or NH 3 .
  • a particularly preferred component (b) is a complex salt of the formula III in which L is unsubstituted or substituted by 1 to 3 C 1 -C 4 -alkyl, benzene, thiophene, benzonitrile, acetonitrile, nitrogen (N 2 ), an unsubstituted or partially or fully fluorinated C 1 -C 4 alcohol, CO, H 2 O or NH 3 .
  • Z 1 - and Z 2 - can each represent a single-charged anion, where Z 1 - and Z 2 - can be the same or different, or Z 1 - and Z 2 - can together represent a double-charged anion represent.
  • Suitable anions are, for example, hydride (H - ), halide (for example Cl - , Br - and I - ), BF 4 - , PF 6 - , SbF 6 - , AsF 6 - , unsubstituted or with C 1 -C 4 - Alkyl, C 1 -C 4 alkoxy, (C 1 -C 4 alkyl) 3 Si or (C 1 -C 4 alkyl) 3 SiO-substituted cyclopentadienyl - , or indenyl ', as well as the anions of oxygen acids.
  • Suitable anions are C 1 -C 12 -, preferably C 1 -C 6 - and particularly preferred C 1 -C 4 alcoholates which are in particular branched, for example correspond to the formula R x R y R z CO - , in which R x H or C 1 -C 10 alkyl, R y C 1 -C 10 alkyl and R z represent C 1 -C 10 alkyl or phenyl. Examples are especially i-propyloxy and t-butyloxy.
  • Suitable anions are C 3 -C 18 -, preferably C 5 -C 14 - and particularly preferably C 5 -C 12 acetylides, which can correspond to the formula R w -C ⁇ C - , where R w is C 1 -C 16 alkyl, preferably ⁇ -branched C 3 -C 12 alkyl, for example formula R x R y R z C-, or unsubstituted or with one to 3 C 1 -C 4 alkyl or C 1 -C 4 Represent alkoxy substituted phenyl or benzyl.
  • Some examples are i-propylacetylide, i- and t-butylacetylide, phenylacetylide, benzylacetylide, 2-methylphenylacetylid, 2-i-propylphenylacetylid, 2-i-propyl-6-methylphenylacetylid, 2-t-butylphenylacetylide, 2,6-di- t-butylphenylacetylide and 2-methyl-6-t-butylphenylacetylide.
  • the anions of oxygen acids can be, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C 1 -C 8 -carboxylic acid, such as, for example, formate, acetate, propionate, butyrate , Benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, sulfonates, such as, for example, methyl sulfonate, ethyl sulfonate, propyl sulfonate, butyl sulfonate, trifluoromethyl sulfonate (triflate), optionally with C 1 -C 4 alkyl, C 1 -C 4 Alkoxy or halogen, especially fluorine, chlorine or bromine substituted phenyl sulfonate or benzyl sulfonate
  • Z 1 - and Z 2 - in the formula III are preferably H - , Cl - , Br - , BF 4 - , PF 6 - , SbF 6 - , AsF 6 - , CF 3 SO 3 - , C 6 H 5 - SO 3 - , p-toluenesulfonate (tosylate), 3,5-dimethylphenylsulfonate, 2,4,6-trimethylphenylsulfonate, 4-trifluoromethylphenylsulfonate or cyclopentadienyl.
  • ROMP catalysts of the formula III are [(cyclohexyl) 3 P] 2 RuCl 2 , [(C 6 H 5 ) 3 P] 3 RuCl 2 , [(C 6 H 5 ) 3 P] 3 (CO) RuH 2 , [(C 6 H 5 ) 3 P] 3 RuCl (cyclopentadienyl), [(cyclohexyl) 3 P] 2 (CH 3 OH) Ru (tosylate) 2 , [(o-tolyl) 3 P] 3 RuCl 2 , [ (CH 3 ) 2 CH] 3 P (cumene) RuCl 2 , (Cyclohexyl) 3 P (cumene) RuCl 2 . and in particular (1-methyl-4-isopropylbenzene) -RuCl 2 P (cyclohexyl) 3 .
  • Suitable fillers which can be used as component (c) in the compositions according to the invention are, for example, metal powder, wood powder, glass powder, glass beads, semimetal and metal oxides, such as SiO 2 (aerosils, quartz, quartz powder, quartz material), corundum and titanium oxide , Semimetal and metal nitrides, such as silicon nitride, boron nitride and aluminum nitride, semimetal and metal carbides (SiC), metal carbonates (dolomite, chalk, CaCO 3 ), metal sulfates (barite, gypsum), stone powder and natural or synthetic minerals mainly from the silicate series such as talc, mica, kaolin, wollastonite, bentonite and others.
  • SiO 2 as aerosils, quartz, quartz powder, quartz material
  • Semimetal and metal nitrides such as silicon nitride, boron nitride and aluminum nitride, semimetal and
  • a metal oxide, carbonate, sulfate or silicate or SiO 2 is preferably used as component (c).
  • quartz powder is particularly preferred.
  • silanes of the formula I are known and can be prepared by known methods. Some of these silanes are commercially available.
  • Preferred silanes of the formula 1 are those in which R is a monovalent organic group having 2 to 100 carbon atoms for C 1 -C 20 alkyl, C 5 -C 20 aryl, C 6 -C 20 aralkyl, C 5 -C 12 -Cycloalkyl, C 2 -C 20 alkoxyalkyl, C 2 -C 20 alkenyl, C 4 -C 25 acryloxyalkyl, C 4 -C 25 methacryloxyalkyl, C 2 -C 20 aminoalkyl, C 4 -C 25 glycidyloxyalkyl , C 7 -C 25 epoxycyclohexylalkyl or the rest of a polysiloxane.
  • Alkyl as R, Y 1 , Y 2 or Y 3 includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the various isomeric pentyl-, hexyl-, heptyl -, Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl groups.
  • Aryl as R, Y 1 , Y 2 or Y 3 preferably contains 6 to 10 C atoms. It can be, for example, phenyl, pentalinyl, indenyl, naphthyl, azulinyl and anthryl.
  • Aralkyl as R, Y 1 , Y 2 or Y 3 preferably contains 7 to 12 C atoms and particularly preferably 7 to 10 C atoms.
  • it can be benzyl, phenethyl, 3-phenylpropyl, ⁇ -methylbenzyl, 4-phenylbutyl and ⁇ , ⁇ -dimethylbenzyl.
  • Cycloalkyl as R, Y 1 , Y 2 or Y 3 is preferably C 5 -C 8 cycloalkyl, in particular C 5 or C 6 cycloalkyl. Some examples are cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • alkoxyalkyl as R, Y 1 , Y 2 or Y 3 are 2-methoxyethyl, 2-ethoxyethyl, 2-methoxypropyl, 3-methoxypropyl, 2-ethoxypropyl and 3-ethoxypropyl.
  • Alkenyl as R includes, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n- Dodec-2-enyl, isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl.
  • acryloxyalkyl and methacryloxyalkyl are 2-acryloxyethyl, 2-methacryloxyethyl, 3-acryloxypropyl and 3-methacryloxypropyl.
  • Suitable aminoalkyl groups are, for example, 2-aminoethyl, 3-aminopropyl, 3-aminobutyl and 4-aminobutyl.
  • Suitable glycidyloxyalkyl groups are 2-glycidylethyl, 3-glycidylpropyl, 3-glycidylbutyl and 4-glycidylbutyl.
  • Epoxycyclohexylalkyl is preferably ⁇ - (3,4-epoxycyclohexyl) ethyl.
  • R in formula I preferably denotes methyl, ethyl, n-octyl, vinyl, 3-mercaptopropyl, 3-aminopropyl, 3-glycidyloxypropyl, 3-acryloxypropyl, 3-methacryloxypropyl, ⁇ - (3,4-epoxycyclohexyl) ethyl, N- ( ⁇ -aminoethyl) -3-aminopropyl, 3-ureidopropyl, 3-isocyanatopropyl, H 2 N-CH 2 CH 2 NH-CH 2 CH 2 NH-CH 2 CH 2 CH 2 -, (CH 3 O) 3 Si-CH 2 CH 2 CH 2 NH-CH 2 CH 2 CH 2 - or a group of the formula
  • Silanes of the formula I in which R is methyl, vinyl, 3-mercaptopropyl or 3-aminopropyl are particularly preferred.
  • Y 1 , Y 2 and Y 3 in formula I are preferably methyl, ethyl, acetyl or 2-methoxyethyl.
  • silanes of the formula I are octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, tris- [3- (trimethoxysilyl) propyl] isocyanurate, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, ⁇ -methacryloxilyl, ⁇ -methacryloxilyl, ⁇ -methacryloxilyl 4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N
  • ⁇ -ureidopropyltrimethoxysilane ⁇ -isocyanatopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-triethoxysilylpropylsuccinic anhydride, 3-methacryloxypropyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, and 3- ( 2-aminoethylamino) propylmethyldimethoxysilane.
  • quartz powder pretreated with a silane of the formula I can also be used.
  • quartz flours pretreated with epoxysilane, alkylsilane or vinylsilane are commercially available, for example, under the names Silbond® W12 EST, Vp W12 VST and Vp W12 SST.
  • compositions according to the invention can vary within wide ranges in the compositions according to the invention.
  • compositions according to the invention preferably contain 15-75% by weight of component (a), 0.001-10.0% by weight of component (b), 20-80% by weight of component (c) and 0.01- 20.0% by weight of component (d), the sum of components (a), (b), (c) and (d) being 100% by weight.
  • Compositions according to the invention are particularly preferred containing 25-65% by weight, in particular 30-50% by weight, of component (a), 0.01-2.0% by weight, in particular 0.1-1.0% by weight .-%, component (b), 30-75 wt .-%, in particular 50-70 wt .-%, component (c) and 0.05-10.0 wt .-%, especially 0.1- 2.0% by weight of component (d).
  • mixtures of substances according to the invention can be prepared in a conventional manner by mixing the components with the aid of known mixing units (e.g. stirrers, rollers).
  • mixing units e.g. stirrers, rollers.
  • composition according to the invention may contain other customary additives, such as Antioxidants, light stabilizers, plasticizers, dyes, pigments, thixotropic agents, toughness improvers, defoamers, antistatic agents, lubricants and mold release agents.
  • additives such as Antioxidants, light stabilizers, plasticizers, dyes, pigments, thixotropic agents, toughness improvers, defoamers, antistatic agents, lubricants and mold release agents.
  • composition according to the invention can contain inert solvents.
  • suitable inert solvents are, for example, protic-polar and aprotic solvents, which can be used alone or in mixtures of at least two solvents. Examples are: ethers (dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl or dimethyl ether, ethylene glycol monoethyl or diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether), halogenated hydrocarbons (methylene chloride, chloroform, 1,2-dichloroethane, 1,1,1-trichloro , 1,2,2-tetrachloroethane), carboxylic acid esters and lactones (ethyl acetate, methyl propionate, ethyl benzoate, 2-methoxyethyl acetate, ⁇ -butyrolactone, ⁇ -valerolactone, pivalolactone),
  • Preferred solvents are aliphatic and aromatic hydrocarbons and mixtures of such solvents.
  • compositions according to the invention are particularly advantageous.
  • metathesis polymerization can be carried out on liquid monomers without the use of a solvent.
  • composition according to the invention can be prepared directly before the polymerization or used as a preformulated mixture.
  • the mixture can be stored as a ready-to-use formulation for a long time before the polymerization, which is advantageous for large-scale use. However, storage in the dark is recommended if the catalyst contains photolabile ligands.
  • a further subject of the invention is a method for producing a metathesis polymer, characterized in that a composition containing components (a) to (d) is heated to a temperature> 40 ° C.
  • the process according to the invention is expediently carried out at a temperature of at least 60 ° C.
  • the process according to the invention is carried out at temperatures from 60 to 300 ° C., preferably 60 to 250 ° C., particularly preferably 60 to 200 ° C. and particularly preferably 70 to 160 ° C.
  • the polymerization can be associated with shaping processes, for example calendering, casting, pressing, injection molding or extrusion processes.
  • shaping processes for example calendering, casting, pressing, injection molding or extrusion processes.
  • materials for the production of moldings of all types and coatings can be produced.
  • Shaping and polymerization are advantageously combined in solvent-free reactive systems, it being possible to use processing methods such as injection molding, extrusion, polymerizations in predetermined forms (if appropriate under pressure).
  • the mixtures produced by the process according to the invention can contain homopolymers, copolymers with a statistical distribution of the structural units, graft polymers, block polymers or crosslinked polymers.
  • the polymers can have an average molecular weight of 500 to 2,000,000 daltons, preferably 1000 to 1,000,000 daltons (determined by means of gel permeation chromatography).
  • the mixtures produced by the process according to the invention are notable in particular for high heat stability, high toughness and mechanical strength and also for excellent electrical properties (low dielectric constant, low loss factor or tan ⁇ value) and are particularly suitable for applications in vacuum casting technology , especially as wrapping material for electrical and electronic components.
  • the hardened casting compounds have good mechanical and dielectric properties and a long service life.
  • the present invention thus also relates to the use of the composition according to the invention as a covering material for electrical or electronic components.
  • Example 2 The procedure described in Example 2 is repeated using Vp W 12 VST instead of Silbond W 12 EST.
  • the properties of the test specimen cured in this way are given in Table 1.
  • Example 2 The procedure described in Example 2 is repeated using Vp W 12 SST instead of Silbond W 12 EST.
  • the properties of the test specimen cured in this way are given in Table 1.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Inorganic Insulating Materials (AREA)
EP96810707A 1995-11-02 1996-10-24 Härtbare Zusammensetzung enthaltend Cycloolefin, Silan und Füllstoff Expired - Lifetime EP0771830B1 (de)

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CA2189311A1 (en) 1997-05-03
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JPH09183833A (ja) 1997-07-15
US6001909A (en) 1999-12-14

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